Treatment of sericeous fibers



Patented Mar. 11, 1947 TREATMENT OF SERICEOUS FIBERS Thomas O. Whitner, Elizabeth, N. J assignor to Chemical Laboratories, Inc., a corporation of New Jersey No Drawing. Application December 26, 1944, Serial No. 569,929

This invention relates to the treatment of cellulosic or vegetable fibers and particularly to such fibers after they have been impregnated with sericeous material.

In m co-pending application, Ser. No. 548,939, filed August 10, 1944, entitled sericeous fibers, of which the instant application is a continuationin-part, I have described and disclosed methods whereby cellulosic or vegetable fibers can be impregnated with sericeous material. Such impregnated fibers have been designated sericeous fibers. Briefly, the procedure comprised dissolving silk fibers in an aqueous solution of an alkylolamine-copper complex containing a small proportion of an alkali metal hydroxide, the proportion of said alkali metal hydroxide being not less than about 0.5% and not more than about 4% of the weight of said aqueous solution, saturating or impregnating vegetable fibers with such a solution, and afterwards washing the impregnated fibers with an aqueous acidic solution. Cellulosic material treated in this manner exhibited properties which distinguished it sharply from the untreated material. For example, the treated cellulosic materials were usually of a cream color and somewhat stiffer or less pliable than the original fibers. Also, impregnation with sericeous bodies increased the dye adsorption capacity of the fibers for substantive, acid or basic dyes, but decreased that for vat dyes.

I have observed that treatment of such impregnated fibers with a saturated aliphatic watersoluble aldehyde, or with a substance yielding such an aldehyde, has an advantageous elfect. For example, after the aldehyde treatment the capacity of the fibers to adsorb acid or basic dyes from solution is greater than that of the impregnated fibers in many instances. Also, this treatment with aldehyde in most cases appears to reduce or lessen the stiffness of the fibers due to the impregnating bodies. Furthermore, although fibers impregnated with sericeous material are immune to some degree from adsorption of vat dyes, after treating such fibers according to this invention they exhibit a greater aifinity for those dyes than do fibers which have not been impregnated with sericeous material.

Cellulosic fibers, after the sericeous material has been impregnated therein, may be. treated with the aldehydic agent in any convenient manner. For example, the fibers may be immersed in an aqueous solution of the aldehyde maintained at atmospheric temperature or higher. Or, the fibers can be saturated with an aqueous solution of the aldehyde and afterwards subjected to a 12 Claims. "(01. 117-161) mild heating operation. In some instances it may be desirable to treat the fibers with the aldehyde while they are in an acidic condition. One procedure whereby this'is possible comprises admixing an acidic agent (e. g., hydrochloric or sulfuric acid) with the aldehyde oraqueous solution thereof before the fibers are immersed therein or saturated therewith. Some care must be exercised, of course, in the selection of the acidic agent as it should not be one which will have any harmful action on the fibers. concentration be sufficiently great to have any deleterious effect on the material undergoing treatment.

The following examples will illustrate my invention.

Example 1.Copper chloride (CuClz-Z-HzO) was dissolved in water, to the solution was added sufiicient monoethanolamine to give a clear blue liquid, and the latter then diluted with water until its concentration was equivalent to 3.75 g. of

the copper salt per 100 cc. of solution.

To a portion of this liquid was added sufiicient sodium hydroxide to react with all the dissolved alkylolamine salt and to furnish a solution containing substantially 1.6 per cent of free or uncombined alkali metal hydroxide. Sufficient silk fibers were dissolved therein to give a 5 per cent solution. The latter was divided into 2 equal parts and in each was immersed, at room temperature, a sample of unbleached cotton cloth for 30 minutes. Afterwards, the samples were removed from the liquids, allowed to drain for a short time and then immersed in an aqueous solution of sulfuric acid until all the copper and alkaline compounds were extracted from the cotton fibers. The latter during immersion in the acid solution were worked gently so as to prevent the solution from becoming locally neutral or even alkaline. Next, the samples were washed With water and air dried. Increase in weight indicated that one portion of cloth contained 2.76 per cent and the other 3.07 per cent of sericeous material.

The goods containing 3.07 per cent of impreg-,

nating material was immersed for 24 hours at room temperature in a solution consisting of 6 volumes of 37 per cent formaldehyde ,and 12 volumes of water. It then was removed from the liquid, washed well with Water and dried at -85 C. j

The two samples containing impregnating sericeous material and also one of the original unbleached goods were dyed separately, using in each instance a bath consisting of 50 parts of Neither should its water to 1 part of cloth and 5 per cent (on weight of cloth) of a red substantive dye. In each in stance, the goods were worked in the respective baths for 5 minutes at room temperature, then the baths were heated to 70 C. over a period of minutes, maintained at that temperature for 30 minutes, and afterwards allowed to cool slowly to room temperature. The samples were removed, rinsed twice with cold. water and allowed to drain and dry.

The untreated portion of cloth dyed to av light; red color, that containing 2.76. percent ofserif-i ceous material dyed to a slightly lighter 'color,

but the sample containing sericeous material and afterwards treated with formaldehyde dyed to a dark red.

Example 2.To a portion of the aqueous-al kylolamine-copper complex solution, as prepared in Example 1, was added sufiicient sodium hy droxide to reactflwith all the dissolved alkylolaa minefitlt andto furnish substantially 215' per cent perature, andafterwards was removed, allowed liquid at room temperature for 75 minutes. The

fabric then was removed, allowed todrain, and washed successively with aqueous sulfuric acid and water in the usual manner and air dried.

Increase in weight of the textile goods indicated it contained 1.56 per cent of impregnating sericeous material.

The impregnated cloth was divided into two portions, one of which was immersed for 2.5

hours in an acid solution of formaldehyde maintained at a temperature of to C. This so-' lution was made by admixing 6 volumes of aqueto drain and then washed successively with aqueous sulfuric acid and water as indicated in, EX;- ample 1. After the cloth had drained and dried,

the increase in weightindicated it contained 5 per cent of sericeous material.

This treated textile material was: divided into 7 2'- portions, one of which was immersed for 48" hours at room temperature in a solution prepared by admixing 5 volumes of 37' per cent aqueous formaldehyde, 15, volumes of water and 1 volume of concentrated aqueous hydrochloric acid. Afterwards, the sample was washed well with wate and dried at -95C.

The two cloths containing sericeous material and also some of the untreated bleached: cloth were dyed separately, using in each instancea and kept, at that temperature for a like period of,

time, Next; the dye liquors were allowedtov cco1.;.

slowly toroom temperature. The dyed, materials were removed, rinsed once with cold wat r and} permitted to drain and air dry..

The untreated cotton cloth dyed to the lightest; color of all the samples. The two cloths contaim 1 ing, sericeous material. were a much darker red in color after completionv of the dyeing operation,

and of these two the one which had been imaj mersed in the aqueous acidified solution of formaldehyde was the deeper red in color. Both-of the impregnated samples were firmer in feel, and 1 stifier than the original bleached somewhat cloth.

Example 3.-.Copper chloride (Ouch-215720) was dissolved; in water,'diethanolamine added until 9. clear 'blue solution obtained, and then the liquid. diluted with water until its concentration,

was equivalent to 12 g. of the copper salt per cc. ofisolution. To the latter was added sufficient potassium hydroxide to react with all of the alkylolamine salt (dissolved therein) and to give substantially 4 per cent of alkali metal hydroxide.

Silk fibers then were dissolved in the alkaline} liquid to give a 6' percent solution. j

Unbleached cotton cloth wasimmerse'd' in this 1 ous 371 per cent formaldehyde, 15 volumes of waterand 1 volumeof concentrated aqueous hydrochloric acid. Afterwards, this aldehyde-treated portion of clothwas washed well with water and The impregnated cloth, the aldehyde-treated cloth and a sample of the original unbleached cloth were dyed; separatelywith a green vatdye.

The dye solution was: prepared by adding 2 parts of the dye (in paste form) to 'lflilflgparts of? water and then dissolving 5 parts of sodium'hydrosulfite and 7.5 parts of sodium carbonate inthe liquid.. When the dye was reduced, each portion of cloth was immersed for 30 minutes at room color was developed, and then vvashed;several;

times with water, and air dried.

The untreated unbleached cloth was dyed to a good green color while only a very light greencolor was imparted to the sample which had been impregnated with sericeous material; The fabric" which had been impregnated and aldehydetrea-ted, however, was dyed to ad'eep 'green color which was of a drakershade of green than that of the dyed untreated cloth.

Example 4.'-The alkylolamine coppersolution containing dissolved silk fibers as preparedirr ample 3 was employed' in this instance; In such a liquid were immersed two samples of a bleached and mercerized cotton yarn. After 16 hours ,at' room temperature these-two; portions of'y jrn' were removed from the liquid, washed successive-- 1y with aqueous sulfuric acid and water, and

dried at 65 to 70 C. Increase-inweightsof textile materials indicated that one sample contained 3.47 per cent of impregnating material and the other 321' per cent; orveiyclosely; the

same proportion;

One of the impregnated samples-was immersed .in a solution consisting of equal volumes of 37" per cent, aqueous formaldehyde and water andto which had been added5 per cent (-by'volume) of concentrated aqueous hydrochloric acid; The"- other impregnated yarn wa-s immersed inasaturated aqueous solution; of paraldehydeto which hadibfeen immersed inthe ITGSDGQtiYS"501111101173): room temperature for. 48 hours; they were washed well with, water anddried atxariqemperaturej of},

worked in the respective baths at room temperae ture; for 5 minutes, after which thetemperature of the bathswas increasedto 70'C: over, a periudg of 30' minutes and" kept at that" temperature for 30 minutes. The baths then were allowed to cool slowly to room temperature. removed, rinsed once with cold Water and permitted to drain and to dry by exposure to the atmosphere.

The bleached and mercerized yarn dyed to a light red color or probably a fairly dark pink. The two impregnated samples, however, dyed to a good full red color, and each was firmer in feel and also somewhat stiffer than the bleached and mercerized yarn.

Example 5.Copper acetate (CU(C2H302) 2-H20) was dissolved in water, then 2-methyl-2-arnino- 1,3-propanedio1 equal to 3.2-5 times the weight of the copper salt was added, and the resulting blue solution was diluted with water until its concentration was equivalent to 2 g. of the copper salt per 50 cc. of solution. Enough sodium hydroxide was dissolved in this liquid to react with the alkylolamine salt and to furnish substantially a 3 per cent solution of the alkali metal hydroxide. Sufficient silk fibers then were dissolved therein to give a 6 per cent solution.

A sample of unbleached cotton yarn was immersed at room temperature for 2 hours in the solution of sericeous material, and afterwards washed successively with aqueous sulfuric acid and water, and dried. Increase in weight of the yarn indicated it contained 5.5 per cent of impregnating sericeous material.

This portion of yarn and also one of the original unbleached material were saturated with aqueous 3'7 per cent formaldehyde and then were heated for 1 hour at 120 to 125 C.

These two treated samples and also one of the untreated yarn Were dyed separately, using in each instance 50 parts of water to 1 part of yarn and 5 per cent (on weight of yarn) of a blue substantive dye. The samples were worked in the respective baths at room temperature for 5 minutes, the temperatures of thebaths then were increased to 70 C. over a period of 30 minutes and maintained at 70 C. for 20 minutes. The baths afterwards were allowed to cool slowly to room temperature. The samples were rinsed with cold water and air-dried.

The lightest colored of these dyed samples was the original unbleached yarn which was very light blue in color. The material which had been treated only with formaldehyde was just very slightly darker in color after dyeing than the dyed original yarn. The impregnated and aldehyde-treated cotton dyed to a dark blue color. Furthermore, it was noted during the dyeing operation that the bath for the last-named sample became very light colored while the other two baths remained a dark blue color, thus indicating the greater adsorptive capacity for dyes of the impregnated and aldehyde-treated fibers.

In the foregoing examples I have illustrated my invention by processes which included impregnating the fibers with sericeous material, then drying them and afterwards treating the impregnated fibers with the aldehydic agent. This drying step is not essential and if desired may be omitted. That is, the fibers after impregnation With sericeous material and while still damp or Wet with water can be subjected to the action of the aldehyde.

I do not wish to be limited to the use of mineral acids, e. g., hydrochloric or sulfuric acid, as the acidic agent. In some cases it may be desirable to use a carboxylic acid, as for example acetic The samples were or formic acid. As an illustration, cellulosic fibers after impregnation with sericeous material can be saturated with an aqueous solution of the aldehyde and which contains a small proportion of acetic acid. Afterwards, the fibers may be subjected to a temperature of to C. until they are substantially dry. Afterwards, the fibers are washed with water to remove any traces or small quantities of acid and/or aldehyde remaining therein. In such a procedure, employment of a mineral acid as the acidic agent would result in considerable tendering or even destruction of the fibers.

My invention has been exemplified by immersion of the sericeous fibers in an aqueous solution of the aldehyde at room or atmospheric temperature or at somewhat higher temperatures of, say, 60 to 70 0. Also, by saturating the sericeous fibers with an aqueous solution of the aldehyde and then subjecting the fibers to a temperature.

of 100 to 0., whereby evaporation of a large proportion or of substantially all of the aldehyde and aqueous liquid occurs. Still another procedure comprises immersion of the sericeous fibers in the solution of the aldehyde and heatin such a solution While it is maintained under pressure. In such instances temperatures of 100 C. or higher may be employed and substantial evaporation of the aldehyde and aqueous liquid prevented. Regardless of the particular method used, I prefer not to exceed a temperature of C., or thereabouts, so as to avoid any possible injury to the fibers undergoing treatment.

As previously mentioned, the aldehydes suitable for my purpose are saturated aliphatic compounds which are appreciably soluble in water,

as for example, formaldehyde, acetaldehyde and propionaldehyde. Polymeric forms of such aldehydes, e. g., paraldehyde, which are soluble in Water in appreciable or substantial proportions are also applicable.

What I claim is:

1. The process for treating cellulose fibers which comprises impregnating said fibers with an aqueous solution of an alkali metal hydroxide and an alkylolamine-copper complex and in which solution are dissolved silk fibers, the proportion of said alkali metal hydroxide being not less than about 0.5% and not more than about 4% the weight of said aqueous solution, washing said impregnated fibers with an aqueous solution of an acidic agent yielding water-soluble salts on reaction with said alkylolamine-copper complex and said alkali metal hydroxide, removing substantially all of said acidic agent and said Watersoluble salts from said cellulose fibers, to give cellulose fibers impregnated with sericeous material, and treating the impregnated fibers with a saturated aliphatic water-soluble aldehyde at a temperature not less than atmospheric and not exceeding 150 C.

2. The method of claim 1, in which the treatment with aldehyde is carried out in the presence of acid.

3. The method of claim 1, in which the aldehyde is formaldehyde.

4. The method of claim 1, in which the alde- 4% the weight .of said-aqueous solution, washing said impregnated fibers with anaqueousesolution of an acidic agent yielding water-soluble .salts with'said alkylolamine-cqppercomplex and said alkali metal hydroxide, removing substantially all of said acidic agent and water-solublie salts from said cellulose fibers, togive'cellulose fibers impregnated with-sericeous' material, and treating the impregnated fibers with a saturated aliphatic water-soluble aldehyde ,at a temperature not lessthan atmospheric and'not exceeding 150 6. The method of claim 5, in which the monohydroxy alkylo'lamine-copper'compleX is monoethanolamine-copper complex.

7. The process for treating 20811111086 fibers which comprises impregnating said fibers with-an aqueous solution ofan alkalimetal hydroxide and a polyhydroxy alkylolaminemopper acomplex and in which solution are dissolved silk "fibers, the proportion .of said alkali metal hydroxide being not lessithan about 0.5% and not more than about 4% the weight of saidaqueous-solution, washing said impregnated fibers with an aqueous solution of an acidic agent yielding water-soluble saltsiwith said alkylolamine-copper complex and said alkali metal hydroxide, removing substantially all of said acidic .agent'and said'water-soluble salts from said cellulose 'fibers, to .give cellulosefibers impregnated with sericeous material,

and treating the impregnated fibers with a .saturated aliphaticwater-solublealdehyde at a temperature not less than atmospheric and not exceeding 150.C.

.8. The process'of claim 7, in which-the polyhydroxy alkylolamin'e-copper complexi's diethanolainine-copper complex.

9. The method of claim 7, in which the 'poly l is 2-.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED' STATES PATENTS Number Name Date 643,923 'Ungnad Feb. 20, 1900 653,014 Ashley July 3, 1900 2,031,245 Bener Feb. 18, 1936 2,238,839 Watkins Apr. 15, 1941 2,262,770 Piana Nov. 18, 1941 FOREIGN PATENTS Number Country Date 465,875 British May 18, 1937 2,676 British -'O c't. 9, 1871 18,119 British 1890 

